AU614707B2 - Creación de Inventos y Patentes con Inteligencia Artificial

AU614707B2 – A method for the protection against water of a laminated resin wall, and a protected laminated resin wall thus obtained
– Google Patents

AU614707B2 – A method for the protection against water of a laminated resin wall, and a protected laminated resin wall thus obtained
– Google Patents
A method for the protection against water of a laminated resin wall, and a protected laminated resin wall thus obtained

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Publication number
AU614707B2

AU614707B2
AU39996/89A
AU3999689A
AU614707B2
AU 614707 B2
AU614707 B2
AU 614707B2
AU 39996/89 A
AU39996/89 A
AU 39996/89A
AU 3999689 A
AU3999689 A
AU 3999689A
AU 614707 B2
AU614707 B2
AU 614707B2
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AU
Australia
Prior art keywords
resin
layer
gel coat
bisphenolic
barrier
Prior art date
1988-08-24
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

Ceased

Application number
AU39996/89A
Other versions

AU3999689A
(en

Inventor
Vincent Guilbaud
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Chantiers Beneteau SA

Original Assignee
Chantiers Beneteau SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1988-08-24
Filing date
1989-08-17
Publication date
1991-09-05

1989-08-17
Application filed by Chantiers Beneteau SA
filed
Critical
Chantiers Beneteau SA

1990-03-01
Publication of AU3999689A
publication
Critical
patent/AU3999689A/en

1991-09-05
Application granted
granted
Critical

1991-09-05
Publication of AU614707B2
publication
Critical
patent/AU614707B2/en

2009-08-17
Anticipated expiration
legal-status
Critical

Status
Ceased
legal-status
Critical
Current

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haloperidol
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Classifications

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H

C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances

C—CHEMISTRY; METALLURGY

C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR

C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR

C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers

C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10S428/00—Stock material or miscellaneous articles

Y10S428/907—Resistant against plant or animal attack

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]

Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree

Y10T428/2495—Thickness [relative or absolute]

Y10T428/24967—Absolute thicknesses specified

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/31504—Composite [nonstructural laminate]

Y10T428/31786—Of polyester [e.g., alkyd, etc.]

Abstract

The invention relates to a laminate based structure, such as a boat hull or a swimming pool, in which the laminate is coated with a barrier-layer or skin coat, in turn coated with a gel layer or gel coat, in which said barrier-layer or skin coat is made of a bisphenol based resin.

Description

ivatent arorneys YOL CHANTIERS BENETEAU S.A.
COWIE, CARTER HENDY Patent Attorneys 71 Queens Road, Melbourne, Victoria, 3004, Australia P/00/Oil PATENTS ACT 1952-1973 Fam~ COMPLETE SPECIFICATION
(ORIGINAL)
FOR OFFICE USE Class: Int. Cl: Application Number: Accepted: Pubised Competeo Sppliicato-ogd Actual Inventor: Vincent GUILBAUD Address for Service: C V E AaT E I Elic» M4 1 PATENT TRADEMARKI ATTORN’,’, 71 QUEENS ROAD, MELBOURNE, 3004, AUSTRALIA Complete Specification for the invention entitled: A METHOD FOR THE PROTECTION AGAINST WIATER OF A LAMINATED RESIN WALL, AND A PROTECTED LAMINATED RESIN WALL THUS OBTAINED.I ‘The following staernent is a full description of this invention. including the beet method of pernrg it k~fm»f to 1 *Note: The description is 10 be type in double speeiMg pica typ faca in an mee not woomdlng 250 mmn V. d~gept wt. ISmm in w~ddi.
on tough whito pow of good quait and it is to be iefltd kwid. thins teM.
1171GM-L 11717-i.C. Tmow~~s C. m -wom inc.. .Cabuu -2 0 METHOD FOR THE PROTECTION AGAINST WATER OF A LAMINATED RESIN WALL, AND A PROTECTED LAMINATED RESIN WALL THUS OBTAINED FIELD OF THE INVENTION The present invention relates to laminated resin walls suitable for use is a structure which is in contact with water for prolonged periods, such as boat hulls, swimming pool walls, basins and containers, etc.
BACKGROUND OF THE INVENTION Laminated resin interior are obtained by applying on the wall of a mold having the required shape mechanically resistance fibers coated with a resin. The result would be a wall in contact with the mold having surface irregularities and the mechanically r.-sistant wall obtained would include pores, which would favor the penetration of water within the thickness of the wall, thereby degrading the constituent resins.
In order to provide a good appearance to the surface of laminated castings, it is known first to coat the surface of the mold with a film forming resin, technically called gel coat. The film forming resins used are polyesters, epoxy resins, etc., which provide semi-permeable membranes. The result is that when they are applied on il laminated resin walls that remain in contact with water, such as swimming pool walls and boat hulls, the outer layers of the gel coat allow the water to penetrate rather quickly into the laminated resin, thereby causing partial separations of the resin layer of the gel coat and the formation of bubbles or blisters. This phenomenon, known as «blistering», lets the water flow to the laminate which is subjected to hydrolysis, so that in addition to the unaesthetic appearance of the blisters, the mechanical characteristics of the laminate are reduced.
In an effort to remedy this disadvantage, it has been proposed to interpose -3 between the laminate and the superficial resin layer or gel coat a layer of resin forming a barrier against the water, called «skin coat». Such a use of two superimposed layers in a laminate limits the choice of the barrier-layer resin, which has to be compatible in order to avoid in particular a risk of separation between the successive layers, particularly under the effect of impacts, as is the case with an intermediate layer of epoxy resin.
So, it has been proposed to provide such a barrier-layer of a vinylester based resin. The use of vinylester based resins, which has been known for a long time in the polyester industry for increasing corrosion resistance, provides a certain increase of the resistance to the penetration of water, while maintaining or even increasing the mechanical strength of the laminate thus coated.
However, it has been recognized that the vinylester based barrier-layer exhibits a certain degree of sensitivity to water and does not delay in a satisfactory way the hydrolysis of the resin of the laminate.
Due to the known high anti-corrosion characteristics of the vinylester resins, the inventor has been led to think that the part played by the barrier against the penetration of water was not tied to the anticorrosive properties of the resin constituting the layer, but resulted from a purely mechanical effect. The vinylester resins which have reactive sites only at the end of their chain, provide in fact a network with a small steric space requirement, thereby facilitating the passage of water through them.
On the basis of this theory, the inventor has studied the behavior as barrierlayer between the gel coat and the laminate of resins having a high steric space requirement, and he has established that a high steric space requirement would greatly 4, 25 reduce the layer permeability.
OBJECTS AND SUMMARY OF THE INVENTION Consequently, the object of the invention is a protection method against water, particularly sea water, of a laminated resin substrate coated on its face iri contact with r- -4the water with a layer of film-forming resin called «gel coat», comprising interposing between the laminated resin substrate and the gel coat layer a barrier-layer, wherein the barrier layer is constituted by a resin having in its chain cyclic nuclei and double reactive bonds imparting to the resin a high steric space requirement.
The typical resins usable within the scope of the invention are resins having a higher steric space requirement than the gel coat resin, such as unsaturated bisphenolic polyesters, the bisphenolic polyesters hydrogen and unsaturated (the bisphenol nucleus of which is saturated) and the unsaturated isophtholic polyesters.
The bisphenolic resins are known for their properties of protection as regards chemical aggressions, but have never been envisioned for forming a barrier against water between a laminated resin and a gel coat layer, such a barrier effect being essentially physico-chemical.
As an example of a bisphenol based resin which can be used preferably for forming the barrier according to the invention, one may cite a bisphenolic polyester resin solid under the trade-mark «STRATYL 1110» and having the following molar formulation: Bisphenol A: 0.2 mole Propylene glycol: 0.8 mole Maleic anhydride: 0.6 mole Phtalic anhydride: 0.4 mole in dilution in a reactive comonomer such as as styrene.
In order to ensure an excellent cohesion between the layers, the invention provides that the gel coat layer is applied on the interior of a mold and the bisphenol based resin layer is applied on the gel coat layer after gelation of the resin, but prior to complete polymerization, that is between 1 hour 30 min and 4 hours after application of the resin layer forming the gel coat. By applying the barrier-layer on the gel layer which is not yet fully polymerized, one ensures a stable bond between the two layers.
Likewise, in order to provide a good cohesion between the barrier-layer and i i i 111the laminate, ite invention provides that the lamination is carried out in a very short time after the deposition of the barrier-layer and prior to the complete polymerization of the barrier-layer.
Advantageously, the barrier-layer and the gel coat layer each have a thickness between 0.30 and 0.45mm. There is thus provided a good preservation of the mechanical properties of the assembly, with limited weight and costs.
The invention also relates to a structure including laminated resin walls, such as boat hulls, swimming pools, etc., the walls being obtained by the above method.
DETAILED DESCRIPTION OF THE INVENTION S 10 The practicing of the invention will be described in more detail hereafter.
A barrier-layer according to the invention has been used for making the hull of a boat having a length of 13 meters, with a total outer surface of 53m 2 composed of 36m 2 of underwater parts wetted by the water and 17m 2 of upper parts.
On the inner wall of the mold has been applied with a gun a propylenediethylene-neopentyl glycol maleoisophthalate based resin, with styrene as a reactive monomer. This resin used for forming the gel coat has been applied with a thickness of 0.9mm on the surface corresponding to the upper parts, viz. 19kg, and of 0.41mm on that corresponding to the underwater parts, viz 18.5kg. The gelation of this gel coat has been provided by 2% of methylethytone peroxyde in a 50% solution in phthalate.
Three hours after application of this gel coat layer which is then polymerized and dry, there has been applied with a gun on the surface corresponding to the underwater parts and with a thickness of 0.46mm, 18kg of a malephthalate of bisphenol A hydrogen and propylene, with styrene as reactive monomer. This resin is sold under the trademark of «STRATYL 1110».
The gelation of this layer has been provided with 2% of a methylethylketone peroxide solution in phthalate. A barrier-layer, called «skin coat» -6has thus been provided on the underwater parts.
After polymerization for 4 hours of this skin coat layer, there was formed on its inner face and on the inner face of the gel coat of the surface corresponding to the upper parts, the polyester based laminated resin wall, reinforced with glass fibers. The hull thus made has proved to be practically impermeable and did not exhibit blisters after several months use in water.
COMPARISON TEST BETWEEN ‘IWO SKIN COATS. ONE VINYLESTER BASED ON THE OTHER ACCORDING TO THE PRESENT INVENTION In order to assess the performance of a gel coat based on maleoisophthalate of S 10 propylene-diethylene-neopentyl glycol associated with vinylester resin or bisphenolic polyester based skin coat layer, the following tests have been carried out.
1. Sensitivity to water of the skin coat constituting resins.
This test has been carried out on plaquettes having a diameter of 8cm, weight of about 25g and a thickness of 5mm. Two plaquettes have been made, one comprising the bisphenolic polyester resin sold under the trademark of «STRATYL 1110», the other comprising a vinylester resin sold under the trademark «ATLAC 580».
The two plaquettes were immersed in water until stabilization of the weight due to the water intake occurred.
The plaquettes were thereafter dried and weighted so as to measure the losses through solubilization of the endogenic compounds under the effect of the hydrolysis I of the product and of the exogenic compounds.
iThe results are shown in Table No. 1.
)u»r sa i-i I I TABLE No. 1 water intake losses through solubilization Plaquette comprising 0.7 0.35 vinylester resin «ATLAC 580» Plaquette comprising bisphenol’c 0.26 0.14 polyester resin «STRATYL 110» 2. Accelerated aging when in contact with water The object of this second series of tests was to compare the aging of a laminated resin protected by ar isophthalic gel coat and by an isophthalic gel coat associated with a skin coat based on «ATLAC» vinylester resin and a skin coat based on «STRATYL» bisphenolic resin. The aging was assesed by the occurrence of blisters on the surface, after immersion in water at 60 0
C.
The results are shown in Table No. 2.
TABLE No. 2 Skin Coat Results No skin coat Occurrence of bubbles after 230 hours ATLAC based Occurrence of bubbles after 910 hours skin coat STRATYL based No bubbles after 1600 hours; test stopped skin coat The bisphenolic based skin coat according to the invention thus notably improves the protection against the penetration of water and hydrolysis.

Claims (13)

1. A structure for prolonged contact with water, comprising a laminated resin wall having an outermost gel coat resin layer, an underlying substrate, and between said gel coat layer and said substrar, a barrier layer consisting essentially of a polymerized resin formed from components having cyclic nuclei and reactive double bonds, said resin having a high steric space requirement relative to vinyl-ester resin and a higher steric space requirement than said gel coat resin layer.

2. A structure for prolonged contact with water, comprising a laminated resin wall having an outermost gel coat resin layer and an underlying substrate, and between said outermost gel coat resin layer and said underlying substrate, a barrier layer consisting essentially of a resin selected from the group consisting of bisphenolic polyesters and unsaturated isophthalic polyesters, said barrier resin having a higher steric space requirement than said gel coat resin layer.

3. The structure according to claim 2, wherein said barrier layer comprises a bisphenolic polyester resin having the following molar formulation: Bisphenol A: 0.2 mole Propylene glycol: 0.8 mole Maleic anhydride: 0.6 mole Phthalic anhydride: 0.4 mole

4. The structure according to claim 2, wherein said bisphenolic polyester is at least partially unsaturated.

The structure according to claim 4, wherein said bisphenolic polyester is a polyester in which the bisphenolic nucleus is saturated.

6. A structure for prolonged contact with water, comprising a laminated resin all formed from a substrate whose outer surface is placed in contact with water, said -9- outer surface having coated thereon a barrier layer of polymerized resin consisting essentially of at least one member selected from the group consisting of bisphenolic polyesters and unsaturated isophthalic polyesters, said layer having a thickness of 0.30 to 0.45mm, and a gel coat resin layer coating said barrier resin layer, said gel coat resin layer having a thickness of 0.30 to 0.45mm and a lower steric space requirement than said barrier resin.

7. The structure according to claim 6, wherein said polymerized resin is an at least partially unsaturated bisphenolic polyester.

8. The structure according to claim 7, wherein said bisphenolic polyester is a resin in which the bisphenol nucleus is saturated.

9. A method for protecting against water a composite resin substrate having an outermost coating of a gel coat resin layer, comprising interposing between the composite resin substrate and the gel coat resin layer a barrier layer consisting essentially of a resin having cyclic nuclei and reactive double bonds, said resin having a high steric space requirement relative to vinylester resin and a higher steric space requirement than said gel coat resin layer.

A method for protecting against water a composite resin substrate having an outermost gel coat resin layer, comprising interposing between the composite resin substrate and the outermost gel coat resin layer a barrier layer consisting essentially of a resin selected from the group consisting of bisphenolic polyesters and unsaturated isophthalic polyesters, said barrier resin having a higher steric space requirement than said gel coat resin layer.

11. The method according to claim 10, wherein said barrier layer comprises a bisphenolic polyester resin having the following molar formulation: Bisphenol A: 0.2 mole Propylene glycol: 0.8 mole Maleic anhydride: 0.6 mole Phthalic anhydride: 0.4 mole.

12. The method according to claim 10, wherein said bisphenolic polyester resin is at least partially unsaturated.

13. The method according to claim 12, wherein said bisphenolic polyester resin is a resin in which the bisphenolic nucleus is saturated. DATED this 12th day of November, 1990.

AU39996/89A
1988-08-24
1989-08-17
A method for the protection against water of a laminated resin wall, and a protected laminated resin wall thus obtained

Ceased

AU614707B2
(en)

Applications Claiming Priority (2)

Application Number
Priority Date
Filing Date
Title

FR8811180A

FR2635716B1
(en)

1988-08-24
1988-08-24

METHOD OF PROTECTING AGAINST WATER OF A LAMINATED RESIN WALL AND WALL OF PROTECTED LAMINATED RESIN THUS OBTAINED

FR8811180

1988-08-24

Publications (2)

Publication Number
Publication Date

AU3999689A

AU3999689A
(en)

1990-03-01

AU614707B2
true

AU614707B2
(en)

1991-09-05

Family
ID=9369494
Family Applications (1)

Application Number
Title
Priority Date
Filing Date

AU39996/89A
Ceased

AU614707B2
(en)

1988-08-24
1989-08-17
A method for the protection against water of a laminated resin wall, and a protected laminated resin wall thus obtained

Country Status (12)

Country
Link

US
(1)

US4959259A
(en)

EP
(1)

EP0356324B1
(en)

JP
(1)

JPH0316679A
(en)

AT
(1)

ATE85069T1
(en)

AU
(1)

AU614707B2
(en)

CA
(1)

CA1327921C
(en)

DE
(1)

DE68904620T2
(en)

DK
(1)

DK398689A
(en)

FR
(1)

FR2635716B1
(en)

IE
(1)

IE62119B1
(en)

NZ
(1)

NZ230324A
(en)

PT
(1)

PT91505B
(en)

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AU695140B2
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1995-03-13
1998-08-06
Mp Hydro Pty Limited
Moulded water containers and process for making same

ATE211497T1
(en)

1997-10-10
2002-01-15
Cook Composites & Polymers

WATER RESISTANT UNSATURATED POLYESTER RESIN BLENDS

ZA9962B
(en)

1998-01-20
1999-07-06
Cook Composites & Polymers
Aromatic polyol end-capped unsaturated polyetherester resins and resin compositions containing the same having improved chemical and/or water resistance.

US20040034333A1
(en)

2002-08-19
2004-02-19
Seese Timothy M.
Dialysis catheters with optimized user-friendly connections

US8168721B2
(en)

2009-02-06
2012-05-01
Eastman Chemical Company
Coating compositions containing tetramethyl cyclobutanediol

US9029461B2
(en)

2009-02-06
2015-05-12
Eastman Chemical Company
Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol

US8163850B2
(en)

2009-02-06
2012-04-24
Eastman Chemical Company
Thermosetting polyester coating compositions containing tetramethyl cyclobutanediol

US8324316B2
(en)

2009-02-06
2012-12-04
Eastman Chemical Company
Unsaturated polyester resin compositions containing 2,2,2,4-tetramethyl-1,3-cyclobutanediol and articles made therefrom

US9029460B2
(en)

2009-02-06
2015-05-12
Stacey James Marsh
Coating compositions containing acrylic and aliphatic polyester blends

JP5600691B2
(en)

2009-02-23
2014-10-01
ハイドラウォールプロプライエタリーリミテッド

Surface composition and application method

US9487619B2
(en)

2014-10-27
2016-11-08
Eastman Chemical Company
Carboxyl functional curable polyesters containing tetra-alkyl cyclobutanediol

US9650539B2
(en)

2014-10-27
2017-05-16
Eastman Chemical Company
Thermosetting compositions based on unsaturated polyesters and phenolic resins

US9598602B2
(en)

2014-11-13
2017-03-21
Eastman Chemical Company
Thermosetting compositions based on phenolic resins and curable poleyester resins made with diketene or beta-ketoacetate containing compounds

US20160340471A1
(en)

2015-05-19
2016-11-24
Eastman Chemical Company
Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol

US20170088665A1
(en)

2015-09-25
2017-03-30
Eastman Chemical Company
POLYMERS CONTAINING CYCLOBUTANEDIOL AND 2,2 BIS(HYDROXYMETHYL) AlKYLCARBOXYLIC ACID

US9988553B2
(en)

2016-02-22
2018-06-05
Eastman Chemical Company
Thermosetting coating compositions

US10011737B2
(en)

2016-03-23
2018-07-03
Eastman Chemical Company
Curable polyester polyols and their use in thermosetting soft feel coating formulations

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1977-05-03
1978-11-21

Ina Seito Co., Ltd.

Reinforced plastic products with decorated surfaces

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(en)

1986-01-29
1988-02-09

The Board Of Governors For Higher Education, State Of Rhode Island

Method of preventing gel coat blistering in fiber glass reinforced polymers

1988

1988-08-24
FR
FR8811180A
patent/FR2635716B1/en
not_active
Expired – Lifetime

1988-10-18
US
US07/259,147
patent/US4959259A/en
not_active
Expired – Fee Related

1989

1989-05-16
NZ
NZ230324A
patent/NZ230324A/en
unknown

1989-08-14
DK
DK398689A
patent/DK398689A/en
not_active
Application Discontinuation

1989-08-15
IE
IE261789A
patent/IE62119B1/en
not_active
IP Right Cessation

1989-08-17
AU
AU39996/89A
patent/AU614707B2/en
not_active
Ceased

1989-08-18
AT
AT89402305T
patent/ATE85069T1/en
not_active
IP Right Cessation

1989-08-18
EP
EP89402305A
patent/EP0356324B1/en
not_active
Expired – Lifetime

1989-08-18
DE
DE8989402305T
patent/DE68904620T2/en
not_active
Expired – Fee Related

1989-08-22
CA
CA000609008A
patent/CA1327921C/en
not_active
Expired – Fee Related

1989-08-22
PT
PT91505A
patent/PT91505B/en
not_active
IP Right Cessation

1989-08-24
JP
JP1218421A
patent/JPH0316679A/en
active
Pending

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Assignee
Title

US4126719A
(en)

1977-05-03
1978-11-21
Ina Seito Co., Ltd.
Reinforced plastic products with decorated surfaces

US4724173A
(en)

1986-01-29
1988-02-09
The Board Of Governors For Higher Education, State Of Rhode Island
Method of preventing gel coat blistering in fiber glass reinforced polymers

Also Published As

Publication number
Publication date

DE68904620T2
(en)

1993-05-19

PT91505B
(en)

1995-05-04

EP0356324A3
(en)

1990-03-21

FR2635716A1
(en)

1990-03-02

IE62119B1
(en)

1994-12-14

AU3999689A
(en)

1990-03-01

DE68904620D1
(en)

1993-03-11

CA1327921C
(en)

1994-03-22

US4959259A
(en)

1990-09-25

IE892617L
(en)

1990-02-24

DK398689A
(en)

1990-02-25

DK398689D0
(en)

1989-08-14

EP0356324B1
(en)

1993-01-27

NZ230324A
(en)

1991-09-25

ATE85069T1
(en)

1993-02-15

FR2635716B1
(en)

1990-11-02

PT91505A
(en)

1990-03-08

EP0356324A2
(en)

1990-02-28

JPH0316679A
(en)

1991-01-24

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